CN112271314A - Flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and preparation method thereof - Google Patents
Flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 tetrathiafulvalene dicarboxylic acid methyl ester Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical compound COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 claims abstract description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910013872 LiPF Inorganic materials 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and a preparation method thereof. The method comprises the steps of firstly, taking carbon disulfide and methyl propiolate as raw materials, synthesizing tetrathiafulvalene dicarboxylic acid methyl ester under the catalysis of tributylphosphine, and then carrying out ester exchange to obtain tetrathiafulvalene dicarboxylic acid ethyl ester. Dissolving tetrathiafulvalene dicarboxylic acid ethyl ester into a solution containing 1mol/L LiPF6And mixing the ethylene carbonate and dimethyl carbonate to obtain the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester. The obtained positive electrolyte has the advantages of high oxidation-reduction potential, high volume specific capacity, good cycling stability and the like.
Description
Technical Field
The invention relates to a flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and a preparation method thereof, and belongs to the field of flow batteries.
Background
In recent years, there have been increasing reports of flow batteries based on organic redox active materials. Organic energy storage materials that have been investigated include nitroxide radical compounds, carbonyl compounds, organosulfur compounds, and the like. The organic compound has the advantages of wide source of synthetic raw materials, environmental protection and the like. The properties of the organic compound, such as solubility, chemical reversibility, oxidation-reduction potential and the like, which are closely related to the performance of the battery can be regulated and controlled through structural modification. In 2016, Liu et al reported that an aqueous flow battery was assembled using 4-hydroxy-2, 2,6, 6-tetramethylpiperidine nitroxide as the positive electrolyte material, commercial viologen as the negative electrolyte material, sodium chloride as the supporting electrolyte, and water as the solvent, the battery voltage reached 1.25V, and had good coulombic efficiency and good cycling ability (Advanced Energy Materials 2016,6, 1501449). But the electrochemical window for water is narrow. Many organic molecules are insoluble in water or have an electrochemical window greater than that of water, and therefore cannot use water as a solvent. The electrochemical window of the organic solvent is wide, so that the electrolyte adopting the organic solvent can broaden the selection and utilization of organic active materials.
Tetrathiafulvalene has received much attention in molecular sensors, molecular switches, nonlinear optics and conductive materials, etc. over the past several decades. Tetrathiafulvalene has mainly some of the following properties: (1) tetrathiafulvalene can be oxidized to monovalent and divalent cations in sequence, and the process is reversible; (2) the substituent on the tetrathiafulvalene molecule can play a role in regulating the oxidation-reduction potential and the solubility; (3) the tetrathiafulvalene cationic radical can be stably present in an organic solvent. Therefore, the development of tetrathiafulvalene-based organic flow batteries is hopeful to realize high oxidation-reduction potential, high volume specific capacity and stable cycle performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a positive electrode electrolyte of a flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester. The flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester has the advantages of high oxidation-reduction potential, high volume specific capacity, stable cycle performance and the like, and has a wide application prospect in the field of organic flow batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester is prepared from tetrathiafulvalene dicarboxylic acid ethyl ester and LiPF6And an organic solvent. The organic solvent is a mixed solution of ethylene carbonate and dimethyl carbonate. The tetrathiafulvalene dicarboxylic acid ethyl ester has the following structural formula:
a preparation method of a positive electrode electrolyte of a flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester comprises the following steps:
(1) adding carbon disulfide and methyl propiolate into anhydrous tetrahydrofuran, adding a catalyst tributylphosphine, reacting for 2-8 hours at the temperature of-100 to-10 ℃ under the protection of argon, carrying out suction filtration, and carrying out forced air drying for 4-12 hours at the temperature of 40-110 ℃, wherein the volume ratio of a crude product is 2: 1, performing chromatography and column chromatography on the mixed solvent of cyclohexane and dichloromethane to obtain tetrathiafulvalene dicarboxylic acid methyl ester, wherein the reaction formula is shown as follows:
(2) adding tetrathiafulvalene dicarboxylic acid methyl ester obtained in the step (1) into absolute ethyl alcohol, adding 0.1-1 mL of concentrated sulfuric acid, reacting for 2-8 hours at the temperature of 20-100 ℃ under the protection of argon, then pouring into deionized water to separate out a precipitate, filtering and collecting the precipitate, and mixing the precipitate with a solvent with a volume ratio of 3: 1, purifying the mixture of cyclohexane and dichloromethane by chromatography and column chromatography to obtain tetrathiafulvalene dicarboxylic acid ethyl ester, wherein the reaction formula is as follows:
(3) firstly preparing LiPF containing 1mol/L6Mixed solution of ethylene carbonate and dimethyl carbonateAnd (3) dissolving the tetrathiafulvalene dicarboxylic acid ethyl ester obtained in the step (2) into the prepared mixed solution at a certain concentration to obtain the tetrathiafulvalene dicarboxylic acid ethyl ester-based flow battery positive electrolyte.
The molar ratio of the carbon disulfide to the methyl propiolate to the tributylphosphine in the step (1) is 1-5: 1-3: 1-3, and the amount of the anhydrous tetrahydrofuran is 10-30 mL per milliliter of carbon disulfide.
The volume of the deionized water in the step (2) is 3-10 times of that of the absolute ethyl alcohol.
The volume ratio of the ethylene carbonate to the dimethyl carbonate in the step (3) is 1-3: 1-3; the concentration of tetrathiafulvalene dicarboxylic acid ethyl ester is 0.005-0.03 mol/L.
In the invention, tetrathiafulvalene dicarboxylic acid ethyl ester is used as an active material of the positive electrode electrolyte, and for the convenience of understanding, the redox mechanism is shown as follows:
the redox reaction of the active material dissolved in the electrolyte is relied on for the energy storage of the flow battery, so that the active material needs to have good solubility, higher theoretical specific mass capacity and good redox reversibility. In addition, the higher the oxidation-reduction potential of the anolyte, the higher the output voltage of the resulting flow battery and the greater the energy density for the same anode. Therefore, the higher the oxidation-reduction potential of the positive electrode electrolyte, the better. According to the invention, tetrathiafulvalene dicarboxylic acid ethyl ester is used as an active substance to prepare the positive electrolyte of the flow battery.
The invention has the beneficial effects that:
1. the tetrathiafulvalene dicarboxylic acid ethyl ester is simple to synthesize, wide in raw material source, green and environment-friendly, and convenient for large-scale production.
2. Tetrathiafulvalene dicarboxylic acid ethyl ester has high solubility in ethylene carbonate and dimethyl carbonate, while tetrathiafulvalene dicarboxylic acid methyl ester, the raw material of which is almost insoluble in ethylene carbonate and dimethyl carbonate.
3. The tetrathiafulvalene unit in tetrathiafulvalene dicarboxylic acid ethyl ester has reversible two-electron redox reaction, and the redox potential is relative to Li+the/Li is more than 3.3V, and the theoretical specific mass capacity reaches 153.84 mAh/g.
4. The positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester is simple to prepare, high in oxidation-reduction potential, high in volume specific capacity and good in circulation stability.
Description of the drawings:
FIG. 1 NMR spectra of ethyl tetrathiafulvalene dicarboxylate prepared in example 2;
fig. 2 cyclic voltammogram of an assembled flow battery of example 8;
fig. 3 is a charge-discharge curve of an assembled flow battery of example 8;
fig. 4 cycle performance of the assembled flow battery of example 8;
fig. 5 a.c. impedance curve of an assembled flow battery of example 8.
Detailed description of the preferred embodiments
The invention is further described below with reference to the figures and examples.
EXAMPLE 1 preparation of Tetrathiafulvalene dicarboxylic acid methyl ester
Adding 10mL (0.165mol) of carbon disulfide and 8.4g (0.1mol) of methyl propiolate serving as raw materials into 80mL of anhydrous tetrahydrofuran, adding 20.2g (0.1mol) of tributylphosphine serving as a catalyst, protecting with argon, reacting at the temperature of-76 ℃ for 4 hours, performing suction filtration, and then drying by blowing at the temperature of 80 ℃ for 6 hours, wherein the volume ratio of a crude product is 2: the cyclohexane of 1 and dichloromethane mixed solvent are chromatographed through a column, and 2.1g of tetrathiafulvalene dicarboxylic acid methyl ester is obtained.
EXAMPLE 2 preparation of Tetrathiafulvalene dicarboxylic acid Ethyl ester
Adding 0.32g (0.001mol) of tetrathiafulvalene dicarboxylic acid methyl ester into 40mL of absolute ethyl alcohol, adding 0.2mL of concentrated sulfuric acid, reacting at 90 ℃ for 4 hours under the protection of argon, adding 400mL of deionized water to precipitate, filtering and collecting the precipitate, and performing precipitation by using a solvent with a volume ratio of 3: the cyclohexane of 1 and methylene dichloride mixed solvent chromatography column purification obtains 0.313g of tetrathiafulvalene dicarboxylic acid ethyl ester.
Examples 3-6 preparation of positive electrolyte for flow batteries based on tetrathiafulvalene dicarboxylate
Preparing 10mL of mixed solution of ethylene carbonate and dimethyl carbonate according to different volume ratios, and adding 1.52g of LiPF into the mixed solution6Then adding a certain mass of tetrathiafulvalene dicarboxylic acid ethyl ester, slightly shaking until the tetrathiafulvalene dicarboxylic acid ethyl ester is dissolved, and standing for later use. The specific charging formulation for each example is shown in table 1.
Table 1 formulation of positive electrolyte for flow batteries based on tetrathiafulvalene dicarboxylate
Preparation of flow battery applying positive electrolyte of flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester in examples 1-4
A CR2032 button cell was used with a lithium metal sheet as the counter electrode and Celgard 2400 as the separator, with a diameter of 17 mm. The electrolyte adopts 1.0M LiPF prepared6And (3) a mixed solution of ethylene carbonate and dimethyl carbonate. The battery assembly process is as follows: in the battery bottom shell, a metal lithium sheet is placed, 25 mu L of electrolyte is dripped on the metal lithium sheet, then a diaphragm is laid, a graphite felt with the diameter of 5mm and the thickness of 1mm is placed, 50 mu L of the anode electrolyte prepared in the embodiments 3-6 is dripped on the graphite felt, and finally a gasket, an elastic sheet and a battery upper cover are sequentially placed, and the battery bottom shell is subjected to punch forming. The prepared flow battery was left for 12 hours, and then was subjected to constant current charging and discharging at a current density of 0.5C (1C ═ 0.536Ah/L), with a charge cut-off voltage of 3.9V and a discharge cut-off voltage of 3.0V. The current density adopted by the cycle test of the prepared flow battery is 0.5C, the number of cycle turns is 100, and the cycle stability of the flow battery is evaluated by the specific capacity retention rate of the cyclic discharge. The specific discharge capacity retention ratio of the cycle is equal to the specific discharge capacity of the 100 th circle/the specific discharge capacity of the 1 st circle multiplied by 100%. The positive electrode electrolyte used in each example and the obtained battery performance are shown in table 2.
Table 2 flow battery performance of flow battery positive electrolyte based on tetrathiafulvalene dicarboxylate
FIG. 1 shows that the nuclear magnetic hydrogen spectrum of tetrathiafulvalene dicarboxylic acid ethyl ester has three absorption peaks of hydrogen, corresponding to ring hydrogen, methylene hydrogen and methyl hydrogen, respectively, and the product is tetrathiafulvalene dicarboxylic acid ethyl ester.
Fig. 2 shows that the flow battery cyclic voltammetry curve of the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester has two oxidation peaks at 3.59V and 3.92V, respectively, and two reduction peaks at 3.32V and 3.64V, respectively, which illustrates that the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester can perform two reversible redox reactions of electron transfer.
Fig. 3 shows the charging and discharging behaviors of the flow battery based on the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester in the voltage range of 3.3V-3.9V, wherein the charging and discharging respectively have two voltage platforms, which indicates that the flow battery based on the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester has higher charging and discharging voltage and stable discharging platform, and is beneficial to high power output.
Fig. 4 shows that the discharge specific capacity and the coulombic efficiency of the flow battery positive electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester are continuously charged and discharged for 100 times, which illustrates that the flow battery positive electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester has a good retention rate of the discharge capacity of the flow battery, has stable cycle performance, and has the coulombic efficiency of more than 90%.
Fig. 5 shows that the alternating-current impedance low-frequency region of the flow battery positive electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester is a semicircle with a smaller diameter, which indicates that the charge transfer resistance is smaller.
Claims (10)
1. Tetrathiafulvalene-based materialThe flow battery positive electrolyte of the ethyl dicarboxylate is characterized by comprising tetrathiafulvalene ethyl dicarboxylate and LiPF6And an organic solvent; the organic solvent is a mixed solution of ethylene carbonate and dimethyl carbonate; the chemical structural formula of the tetrathiafulvalene dicarboxylic acid ethyl ester is shown as follows:
2. the preparation method of the positive electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 1, characterized by comprising the following steps:
(1) adding carbon disulfide and methyl propiolate into anhydrous tetrahydrofuran, adding a catalyst tributylphosphine, protecting with argon, reacting at a certain temperature, performing suction filtration, and performing forced air drying, wherein the volume ratio of a crude product is 2: 1, performing chromatography and column chromatography on the mixed solvent of cyclohexane and dichloromethane to obtain tetrathiafulvalene dicarboxylic acid methyl ester;
(2) adding the tetrathiafulvalene dicarboxylic acid methyl ester obtained in the step (1) into absolute ethyl alcohol, adding 0.1-1 mL of concentrated sulfuric acid, reacting under the protection of argon, pouring into deionized water to separate out a precipitate, filtering, collecting the precipitate, and purifying by using a mixed solvent chromatography column to obtain tetrathiafulvalene dicarboxylic acid ethyl ester;
(3) firstly preparing LiPF containing 1mol/L6Dissolving the tetrathiafulvalene dicarboxylic acid ethyl ester obtained in the step (2) into the prepared mixed solution at a certain concentration to obtain the tetrathiafulvalene dicarboxylic acid ethyl ester-based flow battery positive electrolyte.
3. The method for preparing the flow battery positive electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester is characterized in that the molar ratio of the carbon disulfide, the methyl propiolate and the tributylphosphine in the step (1) is 1-5: 1-3: 1-3, and adding 10-30 mL of anhydrous tetrahydrofuran into each gram of carbon disulfide.
4. The method for preparing the flow battery positive electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 2, wherein the reaction at a certain temperature in the step (1) is specifically as follows: reacting for 2-8 hours at-100 to-10 ℃.
5. The method for preparing the positive electrolyte of the flow battery based on the tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 2, wherein the forced air drying in the step (1) is specifically as follows: and (3) drying the mixture for 4 to 12 hours at the temperature of between 40 and 110 ℃ by blowing.
6. The method for preparing the positive electrolyte of the flow battery based on the tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 2, wherein the reaction in the step (2) is specifically carried out as follows: reacting for 2-8 hours at the temperature of 20-100 ℃.
7. The method for preparing the positive electrode electrolyte of the flow battery based on the tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 2, wherein the volume of the deionized water in the step (2) is 3-10 times that of the absolute ethyl alcohol.
8. The method for preparing the positive electrolyte of the flow battery based on the tetrathiafulvalene dicarboxylic acid ethyl ester, according to claim 2, wherein the volume ratio of the mixed solvent in the step (2) is 3: 1 cyclohexane and dichloromethane.
9. The method for preparing the positive electrode electrolyte of the flow battery based on tetrathiafulvalene dicarboxylic acid ethyl ester, according to claim 2, wherein the volume ratio of the ethylene carbonate to the dimethyl carbonate in the step (3) is 1-3: 1 to 3.
10. The method for preparing the positive electrolyte of the flow battery based on the tetrathiafulvalene dicarboxylic acid ethyl ester according to claim 2, wherein the concentration of the tetrathiafulvalene dicarboxylic acid ethyl ester in the step (3) is 0.005-0.03 mol/L.
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Cited By (2)
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| CN112812096A (en) * | 2021-02-01 | 2021-05-18 | 福州大学 | Tetrathiafulvalene diol compound and preparation method thereof |
| CN113314751A (en) * | 2021-05-25 | 2021-08-27 | 中国科学技术大学 | Aqueous organic flow battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112812096B (en) * | 2021-02-01 | 2021-10-29 | 福州大学 | Tetrathiafulvalene diol compound and preparation method thereof |
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